CN114716306B - Method for hydroformylation of Fischer-Tropsch products - Google Patents

Method for hydroformylation of Fischer-Tropsch products Download PDF

Info

Publication number
CN114716306B
CN114716306B CN202111461093.4A CN202111461093A CN114716306B CN 114716306 B CN114716306 B CN 114716306B CN 202111461093 A CN202111461093 A CN 202111461093A CN 114716306 B CN114716306 B CN 114716306B
Authority
CN
China
Prior art keywords
fischer
pressure
tropsch
temperature
synthesis gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111461093.4A
Other languages
Chinese (zh)
Other versions
CN114716306A (en
Inventor
张安贵
金欣
杨自玲
何雨航
金政伟
石博文
海红莲
刘素丽
朱楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University of Science and Technology
National Energy Group Ningxia Coal Industry Co Ltd
Original Assignee
Qingdao University of Science and Technology
National Energy Group Ningxia Coal Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University of Science and Technology, National Energy Group Ningxia Coal Industry Co Ltd filed Critical Qingdao University of Science and Technology
Priority to CN202111461093.4A priority Critical patent/CN114716306B/en
Publication of CN114716306A publication Critical patent/CN114716306A/en
Application granted granted Critical
Publication of CN114716306B publication Critical patent/CN114716306B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the field of Fischer-Tropsch synthesis and discloses a method for hydroformylation of a Fischer-Tropsch product. The method comprises the following steps: in the presence of a catalyst and a solvent, contacting a Fischer-Tropsch product with synthesis gas to carry out hydroformylation reaction; wherein the Fischer-Tropsch product comprises C 5 ‑C 11 Is a alpha-olefin of (c). The raw material adopted by the method is a coal-based Fischer-Tropsch synthesis product, and the Fischer-Tropsch synthesis product contains C 5 ‑C 11 Alpha-olefins of (C) such that C 5 ‑C 11 When the alpha-olefin is used as the raw material of the hydroformylation, the odd carbon chain alpha-olefin can be provided, and the variety of products is widened.

Description

Method for hydroformylation of Fischer-Tropsch products
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis, in particular to a method for hydroformylation of a Fischer-Tropsch product.
Background
The hydroformylation reaction is also called OXO reaction, and refers to a reaction in which carbon monoxide and hydrogen can be added to an olefin in one step by a transition metal complex catalyst, and an aldehyde having one more carbon atom than the original olefin can be produced with an atom utilization efficiency of 100%. Generally, the linear and branched aldehydes produced by the hydroformylation reaction can be further converted to alcohols by hydrogenation reduction. This is the classical method of industrially producing plasticizer alcohols and surfactant alcohols.
The industry has catalyzed olefin hydroformylation using cobalt-based catalysts, with BASF corporation employing unmodified cobalt carbonyl HCo (CO) 4 As a catalyst, in the actual industrial application process, the unmodified cobalt catalyst usually needs higher reaction temperature (140-180 ℃) and reaction pressure (20-35 MPa) during the hydroformylation reaction, the reaction condition is harsh, and the selectivity of aldehyde in the reaction product is lower (HeckRF, breslowDS.Thereactionofcobalthydrotetracarbonylwitholefins [ J ]]Journ aloftheAmericanChemicalSociety,1961,83 (19): 4023-4027. Further, shell modified cobalt catalysts with trialkyl phosphines, such as tri-n-butyl-phosphorus, to form HCo (CO) 3 (PR 3 ) A catalyst of the type which requires a reduced pressure (5-10 MPa) compared to the BASF process for the hydroformylation of olefins, but which still requires a higher temperature (170-210 ℃) and the selectivity of the aldehydes in the product is still not satisfactory (US 3239569; US 3448157). Compared with the harsh reaction conditions of cobalt catalysts, rhodium catalysts have been attracting attention because of the mildness of the reaction conditions and good selectivity of the reaction products, DAVY company, UCC company, BASF company all use triphenylphosphine as phosphine ligand to modify rhodium catalysts to expect formation of HRh (CO) during the reaction x (PPh 3 ) 4-x The catalyst has a catalytic active center, and the reaction pressure is smaller (usually 1-15 MPa) and the reaction temperature is lower (100-130 ℃) when the catalyst is practically applied in industry (Rhodium catalyzedHydroxymyction [ M)].SpringerScience&BusinessMedia,2002.)。
Linear alpha-olefins as important raw materials for hydroformylation reactions can be produced initially by thermal cracking of paraffins, which can produce large quantitiesAn amount of alpha-olefins, a small amount of alkanes and internal olefins. Wherein, the mixture of internal olefin and alpha-olefin can be subjected to hydroformylation reaction through Co catalyst to further synthesize detergent alcohol; alpha-olefins may also be produced by dehydration of alpha-alkanols. However, these two methods are gradually abandoned by people because the reaction conditions are too severe. Then, people start to adopt a method of steam cracking long-chain alkane and catalytic cracking long-chain alkane to generate alkene and alkyne. C since the 70 th century of 20 th century 4 -C 18 The olefin of (2) is mainly produced by an ethylene oligomerization method provided by a Shell High Olefin Process (SHOP), but the method can only provide alpha-olefin with even carbon chain length to the market by ethylene oligomerization, and it is difficult to provide alpha-olefin with odd carbon chain type except propylene.
Moreover, in the prior art of coal-based Fischer-Tropsch olefin hydroformylation, the carbon chain length of the Fischer-Tropsch olefin used for the hydroformylation reaction is still short, the carbon chain length is limited to propylene and butene, and the normal-to-iso ratio of the product aldehyde is still low.
Disclosure of Invention
The invention aims to solve the problems that the raw materials of the hydroformylation reaction are limited, the normal-to-iso ratio of product aldehyde is still low, and an ethylene oligomerization method cannot obtain odd carbon chain alpha-olefin in the prior art, and provides a Fischer-Tropsch product hydroformylation method.
To achieve the above object, in one aspect, the present invention provides a method for hydroformylation of a fischer-tropsch product, the method comprising:
in the presence of a catalyst and a solvent, contacting a Fischer-Tropsch product with synthesis gas to carry out hydroformylation reaction; wherein the Fischer-Tropsch product comprises C 5 -C 11 Is a alpha-olefin of (c).
The invention provides a method for hydroformylation of Fischer-Tropsch products, which adopts coal-based Fischer-Tropsch synthesis products as raw materials, wherein the Fischer-Tropsch synthesis products contain C 5 -C 11 Alpha-olefins of (C) such that C 5 -C 11 When the alpha-olefin is used as the raw material of the hydroformylation, the odd carbon chain alpha-olefin can be provided, the normal and abnormal ratio of the product aldehyde is high, and the variety of the product is widened.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the invention provides a process for hydroformylation of a Fischer-Tropsch product. The method comprises the following steps:
in the presence of a catalyst and a solvent, contacting a Fischer-Tropsch product with synthesis gas to carry out hydroformylation reaction; wherein the Fischer-Tropsch product comprises C 5 -C 11 Is a alpha-olefin of (c).
In some embodiments of the invention, the weight ratio of the catalyst, the solvent and the fischer-tropsch product is 1 to allow the reaction to proceed efficiently: 8-80:95-1000, preferably 1:30-50:400-450.
In some embodiments of the invention, preferably, C in the Fischer-Tropsch product 5 -C 11 The content of alpha-olefins is 50 to 68 wt.%. Further preferably, the alpha-olefin comprises at least one of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-undecene.
In some embodiments of the present invention, preferably, the Fischer-Tropsch product further comprises pentane, hexane, heptane, octane, nonane, decane, undecane, C 5 Isoolefins (e.g. 2-pentene and/or cyclopentene), C 6 Isoolefins (e.g. 2-hexene), C 7 Isoolefins (e.g. 2-heptene and/or 3-heptene), C 8 Isoolefins (e.g. 3-octene and/or 2, 3-dimethyl-1-hexene), C 9 Isoolefins (e.g. cis-2-nonene and/or 4-nonene), C 10 Isoolefins (e.g., at least one of 2-decene, trans-3-decene, and 5-decene), C 11 At least one of isoolefins (e.g., 2-undecene and/or 3-undecene) and oxygenates.
In the invention, the method can be as followsThe Fischer-Tropsch product is separated into fractions of different carbon chain lengths according to conventional methods, and each fraction is suitable for use in the process of the invention. According to a preferred embodiment of the invention, the Fischer-Tropsch product is Fischer-Tropsch C 5 Fractions of the Fischer-Tropsch C 5 The composition of the fractions is generally: 50-51wt% of 1-pentene, 40-41wt% of pentane and C 5 4-5wt% of isoolefin, 4-5wt% of oxygen-containing compound and 0.8-0.9mgKOH/g of acid value. According to another preferred embodiment of the invention, the Fischer-Tropsch product is C 6 Fractions of the Fischer-Tropsch C 6 The composition of the fractions is generally from 60 to 65% by weight of 1-hexene, from 25 to 30% by weight of hexane, C 6 6-8wt% of isoolefin, 4-5wt% of oxygen-containing compound and 1.7-1.8mgKOH/g of acid value. According to another preferred embodiment of the invention, the Fischer-Tropsch product is C 7 Fractions of the Fischer-Tropsch C 7 The composition of the fractions is generally from 60 to 65% by weight of 1-heptene, from 25 to 30% by weight of heptane, C 7 3-8wt% of isoolefin, 4-5wt% of oxygen-containing compound and 1.4-1.5mgKOH/g of acid value. According to another preferred embodiment of the invention, the Fischer-Tropsch product is C 5 -C 7 Fractions of the Fischer-Tropsch C 5 -C 7 The composition of the fractions is generally from 18 to 20% by weight of 1-pentene, from 20 to 23% by weight of 1-hexene, from 10 to 20% by weight of 1-heptene, C 5 -C 7 30-40wt% of mixed alkane and C 5 -C 7 4-5wt% of mixed isoolefin, 4-5wt% of oxygen-containing compound and 1.4-1.6mgKOH/g of acid value. According to another preferred embodiment of the invention, the Fischer-Tropsch product is C 5 -C 11 Fractions of the Fischer-Tropsch C 5 -C 11 The composition of the fraction is generally 1-pentene 2-5wt%, 1-hexene 10-15wt%, 1-heptene 15-20wt%, 1-octene 18-20wt%, 1-nonene 19-20wt%, 1-decene 0.1-1wt%, 1-undecene 0.1-1wt%, and C 5 -C 11 26.5 to 30 weight percent of mixed alkane and C 5 -C 11 1-2wt% of mixed isoolefin, 4-5wt% of oxygen-containing compound and 1.6-1.8mgKOH/g of acid value.
In the invention, the Fischer-Tropsch product obtaining method comprises the following steps: crude synthesis gas (H) obtained by indirect coal liquefaction 2 The +CO) is subjected to Fischer-Tropsch synthesis (F-T) reaction to generate Fischer-Tropsch products, and the catalyst can be an iron-based catalyst, a cobalt-based catalyst and a nickel-based catalyst, wherein the reaction conditions can beThe inventor of the present invention further found that the components of the Fischer-Tropsch product used in the present invention are complex and may contain acidic substances, which are toxic to rhodium-based catalytic systems and affect the stability of the catalyst, so that the existing catalyst cannot meet the requirements of hydroformylation reaction. To this end, the method further comprises: before the hydroformylation reaction, the Fischer-Tropsch product is mixed with alkali liquor for deacidification, so that the problem of acidosis of an oxo catalyst is effectively solved, the hydroformylation reaction is further promoted, the raw material conversion rate is improved, and the like. Preferably, the acid value of the mixture obtained after the deacidification treatment is not more than 0.05mgKOH/g.
In some embodiments of the present invention, to reduce the emulsification phenomenon and improve the deacidification effect, the weight ratio of the fischer-tropsch product to the alkaline solution is preferably 1:1-2.
In some embodiments of the invention, the Fischer-Tropsch product has an acid number of from 0.79 to 2.85mgKOH/g.
In some embodiments of the invention, preferably, the lye is present in a concentration of 0.5 to 5% by weight.
In some embodiments of the present invention, the alkaline substance in the alkaline solution is not particularly limited, and may be, for example, at least one selected from sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine.
In some embodiments of the invention, the deacidification treatment is performed under stirring conditions to increase the conversion rate of the reaction and the selectivity of aldehyde, and the deacidification treatment conditions include: the temperature is 20-40 ℃, the pressure is 0.01-0.1MPa, the stirring speed is 400-800r/min, and the time is 200-300min.
In some embodiments of the invention, the catalyst is a rhodium compound, with which the positive to negative ratio of the product aldehyde can be up to 30 or more, in order to obtain higher selectivity to linear aldehyde.
In some embodiments of the invention, the catalyst is a rhodium-containing complex, preferably the weight ratio of rhodium precursor to ligand in the catalyst is 1:10-105, more preferably 1:10.2-102.
The rhodium catalyst of the invention can be recycled, the total TON can be up to 60978, the loss of rhodium metal in the recycling process is very little, and the production cost is saved.
In some embodiments of the invention, to prevent oxidation of the catalyst, it is preferred that the rhodium precursor is complexed with the ligand under anaerobic conditions prior to the hydroformylation reaction, and then activated in a reducing atmosphere. In the present invention, "oxygen-free" does not mean an absolute absence of oxygen, but means that the oxygen content is 100ppm by volume or less, but includes an absolute absence of oxygen. The oxygen in the reaction system can be replaced by filling inert gas into the reaction system so as to ensure that the complexation is carried out under the anaerobic condition. In the present invention, the optional range of the kind of the inert gas is wide, for example, one or more of nitrogen, argon and lower hydrocarbon. The reducing atmosphere can be H 2 And/or CO.
In the present invention, the activation is to increase the catalyst activity. In some embodiments of the invention, to enhance catalyst use, preferably, the complexing conditions include: the temperature is 20-40 ℃, the pressure is 0.01-0.1MPa, the stirring speed is 400-800r/min, and the time is 10-15h.
In some embodiments of the invention, to increase catalyst activity, preferably, the activating conditions include: the pressure is 1-7MPa, the temperature is 90-120 ℃, the stirring speed is 400-800r/min, and the time is 0.5-2h.
In some embodiments of the invention, preferably, the rhodium precursor is selected from Rh (acac) (CO) 2 And/or HRh (CO) 4 。
In some embodiments of the invention, preferably, the ligand of the catalyst is selected from a monophosphine ligand or a biphosphine ligand, preferably triphenylphosphine (formula (1), abbreviated PPh 3 ) And/or 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene (structural formula (2), abbreviated as XantPhos). Wherein, the structural formula of triphenylphosphine is:
the structural formula of the 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene is as follows:
in some embodiments of the invention, the catalyst is selected from HRh (CO) 3 (PPh 3 )、HRh(CO) 2 (PPh 3 ) 2 、HRh(CO)(PPh 3 ) 3 And HRh (CO) 2 At least one of (XantPhos).
In some embodiments of the present invention, preferably, the solvent is selected from at least one of toluene, xylene, and benzene.
In some embodiments of the invention, preferably, H in the synthesis gas 2 And the molar ratio of CO is 1-2.
In some embodiments of the invention, the synthesis gas is used in an amount such that the hydroformylation reaction is at a pressure of 1 to 7MPa, preferably 3 to 4MPa, to enhance the reaction.
In some embodiments of the invention, the hydroformylation reaction is carried out under agitation.
In some embodiments of the invention, the hydroformylation reaction conditions include: the temperature is 90-120 ℃, the stirring speed is 400-800r/min, and the time is 1-6h.
In the present invention, after the hydroformylation reaction is completed, the resulting mixture is distilled (for example, may be distilled under reduced pressure) to obtain aldehyde, and the remaining residual liquid is recycled as a catalyst phase.
According to a specific embodiment of the invention, the hydroformylation reaction of the invention is carried out as follows:
(1) Contacting a rhodium precursor with a ligand to complex and activate;
(2) Mixing the Fischer-Tropsch product with alkali liquor for deacidification;
(3) In the presence of the catalyst and the solvent obtained in the step (1), the mixture obtained in the step (2) is contacted with synthesis gas to carry out hydroformylation reaction; specifically, the gas in the high-pressure reaction kettle is replaced by synthesis gas, and then the synthesis gas with a specified pressure (such as 1-7MPa, preferably 3-4 MPa) is filled for hydroformylation reaction.
The present invention will be described in detail by examples. In the following examples and comparative examples, the Fischer-Tropsch product compositions are shown in tables 1-5, and in addition, the various starting materials used were all commercially available, unless otherwise specified.
The composition of the various carbon chain length fractions of each Fischer-Tropsch product is shown in tables 1-5 below:
table 1 shows Fischer-Tropsch C 5 Fraction raw material composition
Table 2 shows Fischer-Tropsch C 6 Fraction raw material composition
Numbering device Component (A) Content/wt%
1 1-hexene 63.74
2 Hexane 25.74
3 C 6 Isomerised olefins 6.19
4 Oxygen-containing compound 4.33
5 Acid value/mgKOH/g 1.71
Table 3 shows Fischer-Tropsch C 7 Fraction raw material composition
Numbering device Component (A) Content/wt%
1 1-heptene 63.28
2 Heptane (heptane) 29.35
3 C 7 Isomerised olefins 3.09
4 Oxygen-containing compound 4.28
5 Acid value/mgKOH/g 1.48
Table 4 shows Fischer-Tropsch C 5 -C 7 Fraction raw material composition
Table 5 shows Fischer-Tropsch C 5 -C 11 Fraction raw material composition
Numbering device Component (A) Content/wt%
1 1-pentene 2.77
2 1-hexene 10.41
3 1-heptene 15.68
4 1-octene 18.6
5 1-nonene 19.67
6 1-decene 0.12
7 1-undecene 0.11
8 C 5 -C 11 Mixed alkanes 26.93
9 C 5 -C 11 Mixed isoolefins 1.35
10 Oxygen-containing compound 4.36
11 Acid value/mgKOH/g 1.69
Example 1
Will 1 mg Rh (acac) (CO) 2 10.2 mg PPh 3 Mixing with 0.866 g toluene, complexing (20 ℃ C., 0.01MPa, stirring speed 400r/min, time 10 h) and activating (1 MPa, 90 ℃ C., stirring speed 400r/min, time 0.5 h), then mixing the activated mixture with 10.165 g of undeacidification Fischer-Tropsch 1-pentene (Fischer-Tropsch C of Table 1) 5 Fraction) was charged into a high-pressure reaction vessel with a temperature controller and a magnetic stirrer, and P was introduced into the vessel H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and a stirring speed of 800rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 2
Will 1 mg Rh (acac) (CO) 2 60 mg PPh 3 After mixing with 0.898 g of toluene, complexation (temperature 40 ℃ C., pressure 0.01MPa, stirring rate 500r/min, time 15 h) and activation (pressure 7MPa, temperature 120 ℃ C., stirring rate 800r/min, time 2 h) were carried out, and the activated mixture was then reacted with 11.02 g of non-deacidified Fischer-Tropsch 1-hexene (Fischer-Tropsch C of Table 2) 6 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1: 2, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 3MPa, reacting for 4 hours at the temperature of 110 ℃ and the stirring speed of 500rpm, rapidly cooling in an ice water bath, decompressing, opening the kettle, sampling, and performing gas chromatography analysis, wherein the analysis result is shown in table 6.
Example 3
Will 1 mg Rh (acac) (CO) 2 102 mg PPh 3 Mixing with 0.91 g toluene, complexing (30 deg.C, 0.05MPa, stirring speed)At a rate of 800r/min for 13 h) and activation (pressure of 3MPa, temperature of 110 ℃, stirring rate of 600r/min for 1 h), the activated mixture was then reacted with 10.13 g of undedeacidified Fischer-Tropsch 1-heptene (Fischer-Tropsch C of Table 3) 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1: 1.2, replacing air for three times, then adding the synthesis gas into a kettle to enable the pressure of the system to be 7MPa, reacting for 6 hours at the temperature of 100 ℃ and the stirring speed of 400rpm, rapidly cooling in an ice water bath, decompressing, opening the kettle, sampling, and performing gas chromatography analysis, wherein the analysis result is shown in Table 6.
Example 4
Will 1 mg Rh (acac) (CO) 2 16.2 mg PPh 3 Mixing with 0.866 g toluene, complexing (30 deg.C, 0.05MPa, 800r/min stirring speed, 13 h) and activating (3 MPa, 110 deg.C, 600r/min stirring speed, 1 h), mixing with 10.165 g of undeacidification Fischer-Tropsch C 5 -C 7 Mixed olefins (Fischer-Tropsch C of Table 4) 5 -C 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 5
Will 1 mg Rh (acac) (CO) 2 18.2 mg PPh 3 Mixing with 0.866 g toluene, complexing (30 deg.C, 0.05MPa, 800r/min stirring speed, 13 h) and activating (3 MPa, 110 deg.C, 600r/min stirring speed, 1 h), mixing with 10.165 g of undeacidification Fischer-Tropsch C 5 -C 11 (Fischer-Tropsch C of Table 5) 5 -C 11 Fraction) of mixed olefins, with temperature controlIn a high-pressure reaction kettle with a magnetic stirrer, P is introduced into the kettle H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 6
Will 1 mg Rh (acac) (CO) 2 10.2 mg PPh 3 And 0.866 g of toluene (30 ℃ C., 0.05MPa, 800r/min stirring rate, 13 h) and activation (3 MPa, 110 ℃ C., 600r/min stirring rate, 1 h) were mixed, and the activated mixture was then mixed with 10.165 g of 5wt% aqueous ammonia solution in an alkali oil weight ratio of 1:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) Fischer-Tropsch 1-pentene (before deacidification, fischer-Tropsch C of Table 1) having an acid number of 0.04mgKOH/g 5 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 7
Will 1 mg Rh (acac) (CO) 2 10.2 mg PPh 3 And 0.866 g of toluene (30 ℃ C., 0.05MPa, 800r/min stirring rate, 13 h) and activation (3 MPa, 110 ℃ C., 600r/min stirring rate, 1 h) were mixed, and the activated mixture was then mixed with 10.165 g of an aqueous 3wt% ammonia solution in an alkali oil weight ratio of 2:1 (temperature 20 ℃ C., pressure 0.1MPa, stirring rate 500r/min, time 240 min) and acid value 0.05mgKOH/g of Fischer-Tropsch 1-pentene (before deacidification, fischer-Tropsch C of Table 1) 5 Fraction), with temperature controller and magnetIn a high-pressure reaction kettle with a force stirrer, P is introduced into the kettle H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 8
Will 1 mg Rh (acac) (CO) 2 10.2 mg PPh 3 After mixing with 0.866 g of toluene, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of a 5wt% diethylamine solution in a base oil weight ratio of 2:1 (temperature 40 ℃ C., pressure 0.05MPa, stirring rate 600r/min, time 250 min) and acid value 0.05mgKOH/g of Fischer-Tropsch 1-pentene (before deacidification, fischer-Tropsch C of Table 1) 5 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 9
Will 1 mg Rh (acac) (CO) 2 51 mg PPh 3 After mixing with 0.866 g of toluene, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of potassium hydroxide solution 3wt% in an alkali oil weight ratio 1:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 400r/min, time 240 min) and acid value 0.02mgKOH/g of Fischer-Tropsch 1-pentene (before deacidification, fischer-Tropsch C of Table 1) 5 Fraction), with temperature controller and magnetIn a high-pressure reaction kettle with a force stirrer, P is introduced into the kettle H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 10
Will 1 mg Rh (acac) (CO) 2 89 mg PPh 3 And 0.866 g of toluene (30 ℃ C., 0.05MPa, 800r/min stirring rate, 13 h) and activation (3 MPa, 110 ℃ C., 600r/min stirring rate, 1 h) were mixed, and the activated mixture was then mixed with 10.165 g of 1wt% potassium hydroxide solution in an alkali oil weight ratio of 2:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) and acid value 0.02mgKOH/g of Fischer-Tropsch 1-pentene (Fischer-Tropsch C of Table 1 before deacidification) 5 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 11
Will 1 mg Rh (acac) (CO) 2 94 mg PPh 3 After mixing with 0.866 g of toluene, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of sodium hydroxide solution 3wt% in a base oil weight ratio 1:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 250 min) Fischer-Tropsch 1-pentene (Fischer-Tropsch C of Table 1 before deacidification) having an acid value of 0.03mgKOH/g 5 Fraction), with a temperature controller andin a high-pressure reaction kettle of a magnetic stirrer, P is introduced into the kettle H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 12
Will 1 mg Rh (acac) (CO) 2 102 mg PPh 3 After mixing with 0.866 g of toluene, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of sodium hydroxide solution 2 wt.%: 1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) Fischer-Tropsch 1-pentene (before deacidification, fischer-Tropsch C of Table 1) having an acid number of 0.04mgKOH/g 5 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 13 (cycle test)
The reaction solution obtained in example 10 was distilled under reduced pressure under argon protection (column bottom temperature 80-115 ℃, column top temperature 35-73.5 ℃, vacuum degree 85kPa, column plate number 23, reflux ratio 3:2), after removing most of the product, a small amount of residual liquid at the bottom of the reactor containing the catalyst remained, transferred to a high-pressure reactor, and 10.165 g of sodium hydroxide solution 2wt% was added according to the weight ratio of alkali oil 2:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) and acid value 0.03mgKOH/g of Fischer-Tropsch 1-pentene (before deacidification, fischer-Tropsch C of Table 1) 5 Fraction), and then the mixture is introduced into a kettleP in H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, after 1 hour of reaction at 100 ℃ with stirring speed of 400rpm, rapid cooling was performed in an ice water bath, then pressure was released, the kettle was opened, and gas chromatography was performed by sampling. This operation was repeated 7 times, and the analysis results are shown in Table 7.
Example 14
Will 1 mg Rh (acac) (CO) 2 56 mg PPh 3 After mixing with 0.866 g of toluene, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of sodium hydroxide solution 2 wt.%: 1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) and acid value 0.04mgKOH/g of Fischer-Tropsch 1-hexene (before deacidification, fischer-Tropsch C of Table 2) 6 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 15
Will 1 mg Rh (acac) (CO) 2 34 mg PPh 3 After mixing with 0.866 g of toluene, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of sodium hydroxide solution 2 wt.%: 1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) and acid value 0.04mgKOH/g of Fischer-Tropsch 1-heptene (before deacidification, fischer-Tropsch C of Table 3) 7 Fraction), high pressure reaction with temperature controller and magnetic stirrerIn the reactor, P is introduced into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 16
Will 1 mg Rh (acac) (CO) 2 102 mg PPh 3 And 0.866 g of xylene, and then carrying out complexation (at a temperature of 30 ℃ C., a pressure of 0.05MPa, a stirring rate of 800r/min, a time of 13 h) and activation (at a pressure of 3MPa, a temperature of 110 ℃ C., a stirring rate of 600r/min, a time of 1 h), and then mixing the activated mixture with 10.165 g of a 3wt% potassium hydroxide solution in an alkali oil weight ratio of 1:1 acid value of 0.04mgKOH/g after deacidification (temperature: 30 ℃ C., pressure: 0.01MPa, stirring rate: 500r/min, time: 240 min) 5 -C 7 Mixed olefins (Fischer-Tropsch C of Table 4 before deacidification) 5 -C 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 17
Will 1 mg Rh (acac) (CO) 2 102 mg PPh 3 After mixing with 0.866 g benzene, complexing (temperature 30 ℃ C., pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activating (pressure 3MPa, temperature 110 ℃ C., stirring rate 600r/min, time 1 h), the activated mixture was then mixed with 10.165 g of 3wt% potassium hydroxide solution in a base oil weight ratio of 1:1 acid value of 0.03mgKOH/g after deacidification (temperature: 30 ℃ C., pressure: 0.01MPa, stirring rate: 500r/min, time: 240 min) 5 -C 11 (Fischer-Tropsch C of Table 5 before deacidification) 5 -C 11 Fraction) of mixed olefins, with addition of a catalyst having a temperatureDegree ofIn a high-pressure reaction kettle of a controller and a magnetic stirrer, P is introduced into the kettle H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 18
Will 1 mg Rh (acac) (CO) 2 After mixing 22.5 mg XantPhos and 0.866 g toluene, complexing (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activating (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h), the activated mixture was then reacted with 10.165 g of non-deacidified Fischer-Tropsch 1-hexene (Fischer-Tropsch C of Table 2) 6 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 19
Will 1 mg Rh (acac) (CO) 2 After mixing 22.5 mg XantPhos and 0.866 g toluene, complexing (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activating (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h), the activated mixture was then reacted with 10.165 g of non-deacidified Fischer-Tropsch 1-heptene (Fischer-Tropsch C of Table 3) 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, and after reacting at 100 ℃ with stirring speed of 400rpm for 1 hour,rapidly cooling in ice water bath, then decompressing, opening the kettle, sampling, and analyzing by gas chromatography, wherein the analysis result is shown in Table 6.
Example 20
Will 1 mg Rh (acac) (CO) 2 Mixing 22.5 mg XantPhos and 0.866 g toluene, complexing (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activating (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h), then mixing the activated mixture with 10.165 g of undeacidification Fischer-Tropsch C 5 -C 7 Mixed olefins (Fischer-Tropsch C of Table 4) 5 -C 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 2 hours at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 21
Will 1 mg Rh (acac) (CO) 2 Mixing 22.5 mg XantPhos and 0.866 g toluene, complexing (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activating (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h), then mixing the activated mixture with 10.165 g of undeacidification Fischer-Tropsch C 5 -C 11 Mixed olefins (Fischer-Tropsch C of Table 5) 5 -C 11 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 2 hours at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 22
Will 1 mg Rh (acac) (CO) 2 22.5 mg XantPhos and 0.866 gToluene was mixed and then subjected to complexation (temperature: 30 ℃, pressure: 0.05MPa, stirring rate: 800r/min, time: 13 h) and activation (pressure: 3MPa, temperature: 110 ℃, stirring rate: 600r/min, time: 1 h), and then the activated mixture was mixed with 10.165 g of a 2wt% sodium hydroxide solution in an alkali oil weight ratio of 2:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) and acid value 0.04mgKOH/g of Fischer-Tropsch 1-hexene (before deacidification, fischer-Tropsch C of Table 2) 6 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:2 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 4MPa, the reaction was carried out for 1 hour at 120 ℃ and stirring speed of 800rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 23
Will 1 mg Rh (acac) (CO) 2 22.5 mg XantPhos and 0.866 g toluene were mixed and then complexed (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activated (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h), the activated mixture then being admixed with 10.165 g of a 2% strength by weight sodium hydroxide solution in an alkaline oil weight ratio of 2:1 (temperature 30 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) and acid value 0.04mgKOH/g of Fischer-Tropsch 1-heptene (before deacidification, fischer-Tropsch C of Table 3) 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1.5, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 3 hours at 110 ℃ with stirring speed of 600rpm, then rapid cooling was carried out in an ice-water bath, then the kettle was opened by pressure relief, and the analysis was carried out by sampling and gas chromatography, and the analysis results were shown in table 6.
Example 24
Will 1 mg Rh (acac) (CO) 2 22.5 mg XantPhos and 0.866 g benzene were mixedAfter the combination, complexation (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activation (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h) were carried out, and then the activated mixture was mixed with 10.165 g of 3wt% potassium hydroxide solution according to an alkali oil weight ratio 1:1 acid value of 0.04mgKOH/g after deacidification (temperature 20 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) 5 -C 7 Mixed olefins (Fischer-Tropsch C of Table 4 before deacidification) 5 -C 7 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 3MPa, the reaction was carried out for 2 hours at 90 ℃ and a stirring speed of 500rpm, then the temperature was rapidly reduced in an ice-water bath, the kettle was opened by pressure relief, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 25
Will 1 mg Rh (acac) (CO) 2 22.5 mg XantPhos and 0.866 g xylene are mixed and then complexed (temperature 30 ℃, pressure 0.05MPa, stirring rate 800r/min, time 13 h) and activated (pressure 3MPa, temperature 110 ℃, stirring rate 600r/min, time 1 h), the activated mixture is then mixed with 10.165 g of 3% by weight potassium hydroxide solution in an alkaline oil weight ratio 1:1 acid value of 0.03mgKOH/g after deacidification (temperature 40 ℃, pressure 0.01MPa, stirring rate 500r/min, time 240 min) 5 -C 11 Mixed olefins (Fischer-Tropsch C of Table 5 before deacidification) 5 -C 11 Fraction), and then charging into a high-pressure reactor equipped with a temperature controller and a magnetic stirrer, and charging P into the reactor H2 ：P CO (molar ratio) =1:1 synthesis gas, air was replaced three times, then synthesis gas was added to the kettle so that the pressure of the system was 1MPa, the reaction was carried out for 1 hour at 100 ℃ and stirring speed of 400rpm, then the temperature was rapidly lowered in an ice-water bath, the pressure was released, the kettle was opened, and the sample was taken for gas chromatography analysis, and the analysis results were shown in table 6.
Example 26
The Fischer-Tropsch product was hydroformylated as in example 1, except that PPh was hydroformylated 3 Replaced by triphenylphosphine sodium tri-m-sulfonate.
Test case
The product aldehydes obtained in the examples and comparative examples were analyzed by gas chromatograph, model GC-2014. Gas chromatography detection conditions: the sample injection amount is 0.2 mu L, the split ratio is 100, the sample injection port temperature is 250 ℃, the detector temperature is 250 ℃, the chromatographic column temperature is 35 ℃ (15 min) -2 ℃/min-200 ℃ (0 min) in a temperature program, and the carrier gas is nitrogen (95 kPa). Chromatographic column: HP-PONA (50 m.times.0.2 mm.times.0.5 μm). Wherein alpha-olefin means C 5 -C 11 The aldehydes in the selectivity of the product aldehydes include C 6 -C 12 Normal aldehyde and isomeric aldehyde of (2), the normal-to-iso ratio of product aldehyde refers to C in the product 6 -C 12 Normal aldehyde and C 6 -C 12 Is used as the catalyst.
The conversion rate and the like are calculated as follows:
the results obtained are shown in Table 6, and the test results of example 13 are shown in Table 7.
TABLE 6
/>
TABLE 7
As can be seen from the results in Table 6, in examples 1-26, the deacidified Fischer-Tropsch olefins had higher feed conversion and higher product aldehyde selectivity than the non-deacidified Fischer-Tropsch olefins, indicating that the deacidified Fischer-Tropsch olefins were better in catalyst activity. As can be seen from the results of examples 6 to 17, the hydroformylation reaction was carried out with triphenylphosphine as ligand and for Fischer-Tropsch C 5 -C 7 Deacidifying the olefin to obtain C 5 -C 7 The conversion of olefins was not less than 89wt%, the selectivity of product aldehyde was not less than 93.7wt%, the normal-to-iso ratio of product aldehyde was not more than 3.3, fischer-Tropsch C of example 17 5 -C 11 The conversion rate of the mixed olefin is only 72.7%, which shows that the ligand triphenylphosphine is suitable for the hydroformylation of Fischer-Tropsch olefins with shorter carbon chains and low requirement on the normal-to-iso ratio of aldehyde. As can be seen from the results of examples 22-25, the preferred ligand 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene is suitable for hydroformylation of Fischer-Tropsch olefins with longer carbon chains, the conversion rate is greater than or equal to 94.8%, the selectivity is greater than or equal to 94.4%, the normal-to-iso ratio is greater than or equal to 28.2, the phosphine ligand of example 26 is triphenylphosphine sodium trimetaphosphate, the conversion rate, the selectivity and the normal-to-iso ratio of the obtained product are poor, and the effect of using triphenylphosphine and 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene ligand is better than that of triphenylphosphine sodium trimetaphosphate. The cyclic test of example 13 shows that after 7 reactions, the conversion rate of the raw materials is reduced, because the catalyst is easy to deactivate at high temperature and is easy to oxidize, and the catalyst is deactivated during reduced pressure distillation, but the selectivity and the positive-to-negative ratio of the product aldehyde are not changed greatly, which means that rhodium loss is very little, and the production cost is saved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (13)

1. A process for the hydroformylation of a fischer-tropsch product, the process comprising:
in the presence of a catalyst and a solvent, contacting a Fischer-Tropsch product with synthesis gas to carry out hydroformylation reaction;
the method further comprises the steps of: before the hydroformylation reaction, mixing a Fischer-Tropsch product with alkali liquor for deacidification;
the deacidification treatment is carried out under the condition of stirring, and the conditions of the deacidification treatment comprise: the temperature is 20-40 ℃, the pressure is 0.01-0.1MPa, the stirring speed is 400-800r/min, and the time is 200-300min;
the catalyst is a rhodium-containing complex; wherein the weight ratio of rhodium precursor to ligand used for preparing the rhodium-containing complex is 1:10-105; the ligand is selected from 4, 5-bis (diphenylphosphine) -9, 9-dimethylxanthene; the rhodium precursor is selected from Rh (acac) (CO) 2 ；
The consumption of the synthesis gas is such that the pressure of the hydroformylation reaction is 1-7MPa;
the hydroformylation reaction is carried out under stirring;
the conditions of the hydroformylation reaction include: the temperature is 90-120 ℃, the stirring speed is 400-800r/min, and the time is 1-6h;
the Fischer-Tropsch product is C 5 -C 11 Fractions of the Fischer-Tropsch C 5 -C 11 The composition of the fractions was: 2-5wt% of 1-pentene, 10-15wt% of 1-hexene, 15-20wt% of 1-heptene, 18-20wt% of 1-octene, 19-20wt% of 1-nonene, 0.1-1wt% of 1-decene, 0.1-1wt% of 1-undecene and C 5 -C 11 26.5 to 30 weight percent of mixed alkane and C 5 -C 11 1-2wt% of mixed isoolefin, 4-5wt% of oxygen-containing compound and 1.6-1.8mgKOH/g of acid value.
2. The process of claim 1, wherein the weight ratio of the catalyst, the solvent and the fischer-tropsch product is 1:8-80:95-1000.
3. The process of claim 1, wherein the weight ratio of the catalyst, the solvent and the fischer-tropsch product is 1:30-50:400-450.
4. The process according to claim 1 or 2, wherein the weight ratio of fischer-tropsch product to lye is 1:1-2.
5. The process according to claim 4, wherein the lye is present in a concentration of 0.5 to 5% by weight.
6. The method according to claim 4, wherein the alkaline substance in the alkaline solution is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine.
7. The method according to claim 1, wherein the acid value of the mixture obtained after the deacidification treatment is 0.05mgKOH/g or less.
8. The process according to claim 1 or 7, wherein the rhodium precursor is complexed with the ligand under anaerobic conditions prior to the hydroformylation reaction and then activated in a reducing atmosphere.
9. The method of claim 8, wherein the complexing conditions comprise: the temperature is 20-40 ℃, the pressure is 0.01-0.1MPa, the stirring speed is 400-800r/min, and the time is 10-15h.
10. The method of claim 8, wherein the activating conditions comprise: the pressure is 1-7MPa, the temperature is 90-120 ℃, the stirring speed is 400-800r/min, and the time is 0.5-2h.
11. The method of any one of claims 1, 2 and 7, wherein the solvent is selected from at least one of toluene, xylene and benzene.
12. The method of any one of claims 1, 2, and 7, wherein H in the synthesis gas 2 And the molar ratio of CO is 1-2.
13. The process of claim 1 wherein the synthesis gas is used in an amount such that the hydroformylation reaction is at a pressure of from 3 to 4MPa.
CN202111461093.4A 2021-11-30 2021-11-30 Method for hydroformylation of Fischer-Tropsch products Active CN114716306B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111461093.4A CN114716306B (en) 2021-11-30 2021-11-30 Method for hydroformylation of Fischer-Tropsch products

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111461093.4A CN114716306B (en) 2021-11-30 2021-11-30 Method for hydroformylation of Fischer-Tropsch products

Publications (2)

Publication Number Publication Date
CN114716306A CN114716306A (en) 2022-07-08
CN114716306B true CN114716306B (en) 2024-01-30

Family

ID=82234782

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111461093.4A Active CN114716306B (en) 2021-11-30 2021-11-30 Method for hydroformylation of Fischer-Tropsch products

Country Status (1)

Country Link
CN (1) CN114716306B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116102412A (en) * 2023-02-14 2023-05-12 国家能源集团宁夏煤业有限责任公司 Method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668651A (en) * 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
CN1168129A (en) * 1995-01-18 1997-12-17 埃克森化学有限公司 Hydroformylation process
CN111348995A (en) * 2020-04-14 2020-06-30 万华化学集团股份有限公司 Method for preparing aldehyde by olefin hydroformylation
CN111646885A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Method for preparing aldehyde based on hydroformylation of Fischer-Tropsch low-carbon hydrocarbon
CN111647427A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Method for increasing carbon chain length of Fischer-Tropsch alpha-olefin
CN112121864A (en) * 2019-06-24 2020-12-25 内蒙古伊泰煤基新材料研究院有限公司 Hydroformylation catalyst and hydroformylation method of long-chain olefin
CN112898140A (en) * 2021-01-21 2021-06-04 四川大学 Method for preparing aldehyde based on internal olefin catalyzed by phosphoramidite phosphine ligand
CN113087601A (en) * 2019-12-23 2021-07-09 内蒙古伊泰煤基新材料研究院有限公司 High-carbon ether preparation method based on Fischer-Tropsch olefins and high-carbon ether phase change material
CN113698281A (en) * 2020-05-21 2021-11-26 中国石油化工股份有限公司 Hydroformylation process

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668651A (en) * 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
CN1168129A (en) * 1995-01-18 1997-12-17 埃克森化学有限公司 Hydroformylation process
CN111646885A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Method for preparing aldehyde based on hydroformylation of Fischer-Tropsch low-carbon hydrocarbon
CN111647427A (en) * 2019-03-04 2020-09-11 内蒙古伊泰煤基新材料研究院有限公司 Method for increasing carbon chain length of Fischer-Tropsch alpha-olefin
CN112121864A (en) * 2019-06-24 2020-12-25 内蒙古伊泰煤基新材料研究院有限公司 Hydroformylation catalyst and hydroformylation method of long-chain olefin
CN113087601A (en) * 2019-12-23 2021-07-09 内蒙古伊泰煤基新材料研究院有限公司 High-carbon ether preparation method based on Fischer-Tropsch olefins and high-carbon ether phase change material
CN111348995A (en) * 2020-04-14 2020-06-30 万华化学集团股份有限公司 Method for preparing aldehyde by olefin hydroformylation
CN113698281A (en) * 2020-05-21 2021-11-26 中国石油化工股份有限公司 Hydroformylation process
CN112898140A (en) * 2021-01-21 2021-06-04 四川大学 Method for preparing aldehyde based on internal olefin catalyzed by phosphoramidite phosphine ligand

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Origin of the Bite Angle Effect on Rhodium Diphosphine Catalyzed Hydroformylation;Lars A. van der Veen 等;《Organometallics》;第19卷;Table6Ligand5 *

Also Published As

Publication number Publication date
CN114716306A (en) 2022-07-08

Similar Documents

Publication Publication Date Title
CN1230406C (en) Multi-stage preparation process of carbonyl synthesizing aldehyde and/or alcohol
Maitlis et al. The role of electrophilic species in the Fischer–Tropsch reaction
CN111646885B (en) Method for preparing aldehyde based on Fischer-Tropsch low-carbon hydrocarbon hydroformylation
CN101903318B (en) One-stage continuous process for hydroformylating higher olefins or olefin mixtures
CN101903316B (en) Multistage continuous process for the hydroformylation of higher olefins or olefin mixtures
CN112724048B (en) Preparation method and application of sulfonate
CN112898140B (en) Method for preparing aldehyde based on internal olefin catalyzed by phosphoramidite phosphine ligand
CN114716306B (en) Method for hydroformylation of Fischer-Tropsch products
CN109456154A (en) A method of fatty aldehyde is prepared by hydroformylation reaction
CN101565353A (en) Preparation method for 2-propyl enanthol
US2816933A (en) Catalyst regeneration in oxo alcohol synthesis
CN111718237B (en) Preparation method of bio-based isomeric tridecanol
CN114426469A (en) Method for preparing alcohol and aldehyde by olefin hydroformylation
CN112898122A (en) Method for preparing isononyl alcohol from mixed octenes
US20200122128A1 (en) Method for producing aliphatic linear primary alcohols
CN104672046B (en) Method of increasing ethylene and propylene yields by freshening C-4 olefins in catalytic cracking or pyrolysis process after separation
US4400299A (en) Oxidative recovery of cobalt oxo catalysts
CN115041233A (en) Hydroformylation catalyst, preparation method and application in preparation of high-carbon aldehyde from Fischer-Tropsch synthetic oil
US2695315A (en) Synthesis of oxygenated organic compounds
CN110372513B (en) Vinyl acetate hydroformylation method
US2757200A (en) Decobalting of oxo aldehydes with nonaqueous oxalic acid
CN112569947B (en) Shape-controllable uniform rod-shaped structure iron/graphene catalyst and preparation method and application thereof
WO2019045809A1 (en) Process for making gamma-branched alcohol
CN112898138B (en) High-value utilization method of Fischer-Tropsch product
CN115400696B (en) Method and device for preparing high-added-value chemicals from synthesis gas

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant